Epoxy resin hardener compositions and epoxy resin compositions containing such hardener compositions

ABSTRACT

An epoxy resin hardener composition including a reaction product of (i) a compound having at least one vicinal epoxy group, and (ii) an amino alcohol; an epoxy resin composition including the epoxy resin hardener composition and a compound having at least one vicinal epoxy group; and a powder coating composition including particles of the epoxy resin hardener composition and particles of a compound having at least one vicinal epoxy group.

CROSS REFERENCE TO RELATED SUBJECT MATTER

This application is a Continuation application of U.S. patentapplication Ser. No. 13/784,142, filed Mar. 4, 2013 (now U.S. Pat. No.8,927,663), which is a Divisional application of U.S. patent applicationSer. No. 12/812,534, having 371(c) date of Aug. 19, 2010 (now U.S. Pat.No. 8,389,652), which is a National Stage Application ofPCT/US2009/030170, filed Jan. 6, 2009, and published as WO2009/094235 onJul. 30, 2009, which claims the benefit of U.S. Provisional ApplicationSer. No. 61/022,955, filed Jan. 23, 2008, the entire contents of whichare incorporated herein by reference.

BACKGROUND OF THE INVENTION

The instant invention is in the field of epoxy resin compositions. Morespecifically, the instant invention relates to compositions forhardening or curing epoxy resins, and especially, epoxy resins useful inpowder coating applications.

Due to their physical and chemical properties such as high resistance tochemical attack and good adhesion to various substrates, epoxy resinsare useful in the preparation of coatings. The epoxy resins can beapplied, for example, from organic or aqueous solutions onto a varietyof different substrates or applied in a powder form to be cured into afilm coating by heating.

Conventionally, in preparing a powder coating using an epoxy resin,particles of a solid epoxy resin are blended with particles of ahardener such as a compound containing one or more reactive phenolichydroxyl groups or one or more amine groups, which diffuse with andreact with the epoxide groups of the epoxy resin to form a hardthermoset coating. For example, an epoxy powder coating has beenprepared in situ on a suitable substrate by applying a mixture ofparticles of solid epoxy resin with particles of a solid epoxy hardenercomposition having more than one phenolic hydroxyl groups and a suitableaccelerant or catalyst to a substrate and subsequently heating thecoated substrate to effect the reaction between the epoxy containingcomponent and the phenolic hydroxyl containing component. If desired,the mixture can also contain dyes, pigments and flow control agents.

Although the adhesion of the coating prepared from the above-describedepoxy resin compositions to a substrate is generally sufficient, theadhesion of the cured epoxy resin coating to various metal substratessuch as a mild steel substrate when the coated substrate is subjected tohumid conditions has been improved by the use of various chemicalmodifications to the epoxy resin compositions as disclosed in JapanesePatent Applications Kokai Nos S59-24762 and H2-105817; U.S. Pat. No.4,678,712; U.S. Pat. No. 7,001,938; and U.S. Patent Application2004/0147690. Despite the above-mentioned advancements in the art, thereremains a need to further improve the adhesion and processing economicsof the cured epoxy resin coating to various metal substrates such as amild steel substrate when the coated substrate is subjected to humidconditions.

SUMMARY OF THE INVENTION

The instant invention provides a solution to the above-stated problem.Use of an epoxy resin hardener composition of the instant inventionprovides improved adhesion of a cured epoxy resin coating to, forexample, a steel substrate. The epoxy resin hardener composition of theinstant invention can also be used at a relatively low temperature.

More specifically, the instant invention is a hardener compositioncomprising a reaction product of (i) a compound having at least onevicinal epoxy group and (ii) an amino alcohol.

In a related embodiment, the instant invention is an epoxy resincomposition comprising (a) a reaction product of a compound having atleast one vicinal epoxy group and an amino alcohol; and (b) a compoundhaving at least one vicinal epoxy group.

And, in another related embodiment, the instant invention is an epoxyresin powder coating composition comprising particles of a reactionproduct of (a) a compound having at least one vicinal epoxy group and anamino alcohol; and (b) particles of a compound having at least onevicinal epoxy group.

In yet another related embodiment, the instant invention is anisocyanate resin solvent-free composition comprising (a) the reactionproduct of a compound having at least one vicinal epoxy group and anamino alcohol; and (b) a compound having at least one vicinal isocyanategroup.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Unless otherwise stated, a reference to a compound or component includesthe compound or component by itself, as well as in combination withother compounds or components, such as mixtures of compounds.

As used herein, the singular forms “a,” “an,” and “the” include theplural reference unless the context clearly dictates otherwise.

Except where otherwise indicated, all numbers expressing quantities ofingredients, reaction conditions, and so forth used in the specificationand claims are to be understood as being modified in all instances bythe term “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that may vary depending upon thedesired properties sought to be obtained by the present invention. Atthe very least, and not to be considered as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should be construed in light of the number ofsignificant digits and ordinary rounding conventions.

Additionally, the recitation of numerical ranges within thisspecification is considered to be a disclosure of all numerical valuesand ranges within that range. For example, if a range is from about 1 toabout 50, it is deemed to include, for example, 1, 7, 34, 46.1, 23.7, orany other value or range within the range.

The particulars shown herein are by way of example and for purposes ofillustrative discussion of the embodiments of the present invention onlyand are presented in the cause of providing what is believed to be themost useful and readily understood description of the principles andconceptual aspects of the present invention. In this regard, no attemptis made to show embodiments of the present invention in more detail thanis necessary for the fundamental understanding of the present invention,the description making apparent to those skilled in the art how theseveral forms of the present invention may be embodied in practice.

In one embodiment, the instant invention is a composition useful as anepoxy resin hardener comprising a reaction product of (i) a compoundhaving at least one vicinal epoxy group; and (ii) an amino alcohol.

Epoxy Resin Hardener Composition

Component (i) of the epoxy resin hardener composition can be anywell-known epoxy resin. The term “epoxy resin” herein means acomposition which possesses one or more vicinal epoxy groups permolecule, i.e. at least one 1,2-epoxy group per molecule. In general,the epoxy resin compound may be a saturated or unsaturated aliphatic,cycloaliphatic, aromatic or heterocyclic compound which possesses atleast one 1,2-epoxy group. Such compound can be substituted, if desired,with one or more non-interfering substituents, such as halogen atoms,hydroxy groups, ether radicals, lower alkyls and the like.

The epoxy resins useful in the present invention may includemonoepoxides, diepoxides, polyepoxides or mixtures thereof. Illustrativecompounds useful in the practice of the instant invention are describedin the Handbook of Epoxy Resins by H. E. Lee and K. Neville published in1967 by McGraw-Hill, New York; and U.S. Pat. No. 4,066,628, both ofwhich are incorporated herein by reference.

The compound having at least one vicinal epoxy group may comprise acompound having two vicinal epoxy groups. For example, particularlyuseful compounds which can be used in the practice of the presentinvention are epoxy resins having the following formula:

wherein n has an average value of generally 0 or more, preferably from 0to about 100, and more preferably from about 0.1 to about 50.

The epoxy resins useful in the present invention may include, forexample, the glycidyl polyethers of polyhydric phenols and polyhydricalcohols. As an illustration of the present invention, examples of knownepoxy resins that may be used in the present invention, include forexample, the diglycidyl ethers of resorcinol, catechol, hydroquinone,bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenylethane), bisphenol F, bisphenol K, tetrabromobisphenol A,phenol-formaldehyde novolac resins, alkyl substitutedphenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins,cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins,dicyclopentadiene-substituted phenol resins tetramethylbiphenol,tetramethyl-tetrabromobiphenol, tetramethyltribromobiphenol,tetrachlorobisphenol A; and any combination thereof.

Examples of diepoxides particularly useful in the present inventioninclude diglycidyl ether of 2,2-bis(4-hydroxyphenyl) propane (generallyreferred to as bisphenol A) and diglycidyl ether of2,2-bis(3,5-dibromo-4-hydroxyphenyl) propane (generally referred to astetrabromobisphenol A). Mixtures of any two or more diepoxides can alsobe used in the practice of the present invention.

Other diepoxides which can be employed in the practice of the presentinvention include the diglycidyl ethers of dihydric phenols, such asthose described in U.S. Pat. Nos. 5,246,751; 5,115,075; 5,089,588;4,480,082 and 4,438,254, all of which are incorporated herein byreference; or the diglycidyl esters of dicarboxylic acids such as thosedescribed in U.S. Pat. No. 5,171,820, incorporated herein by reference.Other suitable diepoxides include for example,αω-diglycidyloxyisopropylidene-bisphenol-based epoxy resins such asthose commercially known as D.E.R.® 300 and 600 series epoxy resins,which are available products from The Dow Chemical Company.

The epoxy resins which can be employed in the practice of the presentinvention also include epoxy resins prepared either by reaction ofdiglycidyl ethers of dihydric phenols with dihydric phenols or byreaction of dihydric phenols with epichlorohydrin (also known as “taffyresins”).

Preferred epoxy resins useful in the present invention include, forexample, the diglycidyl ethers of bisphenol A; 4,4′-sulfonyldiphenol;4,4-oxydiphenol; 4,4′-dihydroxybenzophenone; resorcinol; hydroquinone;9,9′-bis(4-hydroxyphenyl)fluorene; 4,4′-dihydroxybiphenyl or4,4′-dihydroxy-α-methylstilbene and the diglycidyl esters of thedicarboxylic acids mentioned previously.

Other useful epoxide compounds which can be used in the practice of thepresent invention are cycloaliphatic epoxides. A cycloaliphatic epoxideconsists of a saturated carbon ring having an epoxy oxygen bonded to twovicinal atoms in the carbon ring for example as illustrated by thefollowing general formula:

wherein R is a hydrocarbon group optionally comprising one or moreheteroatoms (such as, without limitation thereto Cl, Br, and S), or anatom or group of atoms forming a stable bond with carbon (such as,without limitation thereto, Si, P and B) and wherein n is greater thanor equal to 1.

The cycloaliphatic epoxide may be a monoepoxide, a diepoxide, apolyepoxide, or a mixture of those. For example, any of thecycloaliphatic epoxide described in U.S. Pat. No. 3,686,359,incorporated herein by reference, may be used in the present invention.As an illustration, the cycloaliphatic epoxides that may be used in thepresent invention include, for example,(3,4-epoxycyclohexyl-methyl)-3,4-epoxy-cyclohexane carboxylate,bis-(3,4-epoxycyclohexyl) adipate, vinylcyclohexene monoxide andmixtures thereof.

Component (ii) of the epoxy resin hardener composition can be anywell-known aminoalchohol. Generally, the aminoalcohol useful in thepresent invention contains amine groups that are preferably primaryamine groups. However, aminoalcohols containing secondary amines groupsare also useful in the present invention. The amino alcohol ispreferably an amino polyol.

For example, the aminoalcohol useful in the present invention may beselected from the group consisting of monoethanolamine;2-amino-2-hydroxymethyl-1,3-propanediol;2-amino-2-methyl-1,3-propanediol; diethanolamine and mixtures thereof.Preferably, 2-amino-2-hydroxymethyl-1,3-propanediol is used in thepresent invention.

The hardener resin composition of the present invention, in general,contains an amount of component (i) and component (ii) wherein the moleratio of the amine groups of the amino alcohol to the epoxy groups ofthe epoxy resin compound having at least one vicinal epoxy group is inthe range of from about 25:1 to about 1:1, preferably from about 10:1 toabout 1:1, more preferably from about 5:1 to about 1:1, even morepreferably from about 3:1 to about 1:1, and most preferably from about2:1 to about 1:1.

The resulting resin hardener composition of present inventionadvantageously has a softening point of from about 30° C. to about 150°C. which allows the composition to be used with various compounds and invarious applications.

For example, the resin hardener composition of the present invention maybe useful as an hardener for one or more of the compounds selected fromepoxy-, isocyanate-, carboxylic acid-, vinyl- and acrylic-functionalresins.

In one embodiment of the present invention, the resin hardenercomposition of the present invention comprises a composition which isfree of residual bisphenol A; induces no foaming; and contains lessvolatiles when a high molecular weight alkanolamine is used in thecomposition. For example, the molecular weight of the high molecularweight alkanolamine may be from about 150 Da to about 10,000 Da.

In another embodiment the resin hardener composition of the presentinvention comprises a composition which is dispersible in water. Thecomposition which is dispersible in water may also be useful to emulsifyepoxy resins without the use of a solvent.

The resin hardener composition of the present invention may be used invarious applications including for example, coating applications,adhesives application or composites applications. In one particularembodiment the resin hardener may be used for a heat-cured epoxycoating.

In yet another embodiment, the resin hardener composition of the presentinvention may be used as a cross-linker for an epoxy resin; wherein theepoxy resin is a high molecular epoxy resin having a molecular weight offrom about 300 Da to about 10,000 Da; wherein the resin hardenercomposition may be formulated in the absence of a solvent and adispersion; and wherein the resin hardener composition may beformaldehyde-free.

Epoxy Resin Composition

In general, a typical epoxy resin composition comprises one or moreepoxy resins and an epoxy resin hardener. The epoxy resin hardenerreacts with the epoxy resin, often at an elevated temperature, toproduce a cured epoxy resin. Prior art epoxy resin hardeners include,for example, aliphatic and aromatic amine based hardeners and phenolicbased hardeners. Epoxy resin compositions also frequently contain acatalyst or an “accelerator”, such as 2-methylimidazole, to increase therate of reaction between the epoxy resin composition and the epoxy resinhardener at any given temperature.

An embodiment of the present invention includes a thermosettable epoxyresin composition comprising (a) an epoxy resin hardener comprising areaction product of (i) a compound having at least one vicinal epoxygroup, and (ii) an amino alcohol; and (b) a compound having at least onevicinal epoxy group.

The reaction product, component (a) of the epoxy resin composition, maybe the epoxy resin hardener composition described above comprising areaction product of (i) a compound having at least one vicinal epoxygroup, and (ii) an amino alcohol.

Component (i), a compound having at least one vicinal epoxy group,useful for preparing component (a) of the epoxy resin composition, mayinclude any of the epoxy resins described above with reference to theepoxy resin hardener composition.

Component (ii), an amino alcohol, useful for preparing component (a) ofthe epoxy resin composition, may include any of the amino alcoholspreviously described above with reference to the epoxy resin hardenercomposition.

Component (b), a compound having at least one vicinal epoxy group whichcan be used for preparing the epoxy resin composition, may include anyone or more of the epoxy resins described above with reference to theepoxy resin hardener composition. The epoxy component (b) may be thesame, or different from, the epoxy resin component (i).

The epoxy resin composition of the present invention may containoptional components such as for example a co-curing agent (co-hardener)well known to those skilled in the art, in addition to, and differentfrom, the epoxy resin hardener composition of the present invention.Co-curing agents useful in the present invention are those compoundsknown to the skilled in the art to react with epoxy resins to form curedfinal products. In one embodiment, the epoxy resin composition of thepresent invention further comprises a co-curing agent.

Examples of co-curing agents useful in the present invention include,for example, amino compounds such as dicyandiamide, DDS, DMA, phenolichardeners such as phenol novolacs, bisphenol-A novolacs, cresolnovolacs, and two functional phenolic hardeners such as D.E.H. 85, D.EH.87 and D.E.H. 90.

In one embodiment, the co-curing agent, utilized in the composition ofthe present invention includes at least one hardener compound with atleast one phenolic hydroxyl functionality, a hardener compound capableof generating at least one phenolic hydroxyl functionality, or mixturesthereof. Preferably, the co-curing agent is a compound or a mixture ofcompounds with a phenolic hydroxyl functionality.

Examples of compounds with a phenolic hydroxyl functionality (thephenolic co-curing agent) include compounds having an average of one ormore phenolic groups per molecule. Suitable phenol co-curing agentsinclude dihydroxy phenols, biphenols, bisphenols, halogenated biphenols,halogenated bisphenols, alkylated biphenols, alkylated bisphenols,trisphenols, phenol-aldehyde resins, phenol-aldehyde novolac resins,halogenated phenol-aldehyde novolac resins, substituted phenol-aldehydenovolac resins, phenol-hydrocarbon resins, substitutedphenol-hydrocarbon resins, phenol-hydroxybenzaldehyde resins, alkylatedphenol-hydroxybenzaldehyde resins, hydrocarbon-phenol resins,hydrocarbon-halogenated phenol resins, hydrocarbon-alkylated phenolresins, or combinations thereof. Preferably, the phenolic co-curingagent includes substituted or unsubstituted phenols, biphenols,bisphenols, novolacs or combinations thereof.

The co-curing agent of the present invention may be selected from, forexample, phenol novolac, bisphenol A novolac, bisphenol A,tetrabromobisphenol A and mixtures thereof.

The co-curing agent may also include any of the multi-functionalphenolic cross-linkers described in U.S. Pat. No. 6,645,631 Column 4,lines 57-67 to Column 6 lines 1-57, incorporated herein by reference.

Examples of co-curing agents capable of generating phenolic hydroxylfunctionalities are monomeric and oligomeric benzoxazines andpolybenzoxazines, and the like. By “generating” herein it is meant thatupon heating the co-curing agent compound, the co-curing agent compoundtransforms into another compound having phenolic hydroxylfunctionalities, which acts as a co-curing agent; wherein the hydroxylfunctionalities can further reaction with the epoxy resin similar to thephenolic co-curing agents defined above. Examples of the co-curingagents may also include compounds which form a phenolic cross-linkingagent upon heating, such as for example, species obtained from heatingbezoxazines as described in U.S. Pat. No. 6,645,631, incorporated hereinby reference. Examples of such components also include benzoxazine ofphenolphthalein, benzoxazine of bisphenol-A, benzoxazine of bisphenol-F,benzoxazine of phenol novolac and the like. Mixtures of such compoundsdescribed above may also be used.

In another embodiment, one or several co-curing agents that do notcontain phenolic hydroxyl functionality or capable of generatingphenolic hydroxyl functionality may be present in the epoxy resincomposition of the present invention. Such co-curing agents include, butare not limited to, for example, amino-containing compounds, such asamines and dicyandiamide, and carboxylic acids and carboxylicanhydrides, such as styrene-maleic anhydride polymer; and mixturesthereof.

Preferably, the molar ratio of the hardener composition of the presentinvention to the co-curing agent (the molar ratio is calculated based onthe active groups capable of reacting with epoxides) is between about100% and about 50% preferably between about 50% and about 0.1%, morepreferably between about 20% and about 0.5%, and even more preferablybetween about 100% and about 0%. Preferably, the weight ratio of thehardener composition of the present invention to co-curing agent isbetween about 100% and about 50%, more preferably between about 50% andabout 1%, even more preferably between about 20% and about 1%, and mostpreferably between about 100% and 0%.

The ratio of the hardener composition of the present invention to epoxyresin is preferably suitable to provide a fully cured resin. The amountof the hardener composition of the present invention which may bepresent may vary. In one embodiment, the molar ratio between the epoxygroups of the epoxy resin Component (b) and the reactive hydrogen groupsof the hardener composition of the present invention Component (a) isbetween about 2 and about 0.5, preferably between about 1.5 and about 1,and more preferably between about 1.3 and about 1. If a co-curing agentis used in combination with the hardener composition of the presentinvention, then the molar ratios described above should be based on thecombination of the hardener composition and co-curing agent.

Accelerators, also referred to as catalysts, may optionally be utilizedin the epoxy resin composition of the present invention. Acceleratorsinclude those compounds which catalyze the reaction of the epoxy resinwith the hardener composition of the present invention (and/or theco-curing agent when present). In one embodiment, the epoxy resincomposition of the present invention further comprises an accelerator.

For example, accelerators useful in the present invention includecompounds containing amine, phosphine, heterocyclic nitrogen, ammonium,phosphonium, arsonium or sulfonium moieties; and mixtures thereof. Morepreferably, the accelerators can be heterocyclic nitrogen andamine-containing compounds and even more preferably, the acceleratorsare heterocyclic nitrogen-containing compounds. Heterocyclicnitrogen-containing compounds useful as accelerators includeheterocyclic secondary and tertiary amines or nitrogen-containingcompounds such as, for example, imidazoles, imidazolidines,imidazolines, bicyclic amidines, oxazoles, thiazoles, pyridines,pyrazines, morpholines, pyridazines, pyrimidines, pyrrolidines,pyrazoles, quinoxalines, quinazolines, phthalazines, quinolines,purines, indazoles, indazolines, phenazines, phenarsazines,phenothiazines, pyrrolines, indolines, piperidines, piperazines, as wellas quaternary ammonium, phosphonium, arsonium or stibonium, tertiarysulfonium, secondary iodonium, and other related “onium” salts or bases,tertiary phosphines, amine oxides, and combinations thereof. Imidazolesas utilized herein include imidazole, 1-methylimidazole,2-methylimidazole, 4-methylimidazole, 2-ethylimidazole,2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole,1-benzyl-2-methylimidazole, 2-heptadecyl imidazole,4,5-diphenylimidazole, 2-isopropylimidazole, 2,4-dimethyl imidazole,2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole andthe like; and mixtures thereof. Preferred imidazoles include2-methylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole; andmixtures thereof.

Among preferred tertiary amines that may be used as accelerators arethose mono- or polyamines having an open chain or cyclic structure whichhave all of the amine hydrogen replaced by suitable substituents, suchas hydrocarbon radicals, and preferably aliphatic, cycloaliphatic oraromatic radicals. Examples of these amines include, among others,methyl diethanolamine, triethylamine, tributylamine,benzyl-dimethylamine, tricyclohexyl amine, pyridine, quinoline, and thelike; and mixtures thereof. Preferred amines are the trialkyl andtricycloalkyl amines, such as triethylamine,tri(2,3-dimethylcyclohexyl)amine, and the alkyl dialkanol amines, suchas methyl diethanolamine and the trialkanolamines such astriethanolamine. Weak tertiary amines, e.g., amines that in aqueoussolutions give a pH less than 10, are particularly preferred. Especiallypreferred tertiary amine accelerators are benzyldimethylamine andtris-(dimethylaminomethyl) phenol.

Imidazolines as utilized herein include 2-methyl-2-imidazoline,2-phenyl-2-imidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline,2-isopropylimidazole, 2,4-dimethyl imidazoline,2-phenyl-4-methylimidazol-ine, 2-ethylimidazoline,2-isopropylimidazoline, 4,4-dimethyl-2-imidazolin-e,2-benzyl-2-imidazoline, 2-phenyl-4-methylimidazoline and the like; andmixtures thereof.

Optionally, the curable epoxy resin composition of the present inventionmay further contain other components typically used in an epoxy resincompositions, particularly for making powder coatings; and which do notdetrimentally affect the properties or performance of the curable epoxyresin composition of the present invention, or the final cured producttherefrom. For example, other optional components useful in the epoxyresin composition may include, but not limited to, toughening agents;curing inhibitors; other reaction accelerators, fillers; wetting agents;colorants; flame retardants such as antimony oxide, octabromodiphenyloxide, decabromodiphenyl oxide, phosphoric acid; solvents;thermoplastics; processing aids; fluorescent compound; such astetraphenolethane (TPE) or derivatives thereof; UV blocking compounds;dyes; pigments; surfactants; flow modifier; flow control agents;viscosity controller; plasticizers; other optional additives commonlyemployed as additives for epoxy resin compositions as is known in theart; and mixtures thereof.

The other optional components used in the epoxy resin composition of thepresent invention may be used in an effective amount to provide theintended property to the epoxy resin composition. For example, theoptional components may be generally employed in an amount of from about0.05 wt % to about 40 wt %.

The curable epoxy resin composition of present invention may be used invarious applications including for example, coatings, adhesives andcomposites. In one embodiment, the epoxy resin composition may containan alkanolamine in the polymer chain modifiable with acrylic acids; andwherein the composition may be useful for UV cure applications.

The curable or hardenable epoxy resin composition of the presentinvention disclosed herein, which may be useful as a coatingcomposition, may be prepared by admixing the components aforementionedabove including, for example, at least one epoxy resin and at least oneepoxy resin hardener composition of the present invention and optionallya co-curing agent.

The curable epoxy resin composition may be prepared by admixing all ofthe components of the composition together in any order. Alternatively,the curable epoxy resin composition of the present invention can beproduced by preparing a first composition comprising the epoxy resincomponent and a second composition comprising the hardener compositioncomponent. All other components useful in making the epoxy resincomposition may be present in the same composition, or some may bepresent in the first composition, and some in the second composition.The first composition is then mixed with the second composition to formthe curable epoxy resin composition. The epoxy resin composition mixtureis then cured to produce an epoxy resin thermoset material. Preferably,the curable epoxy resin composition is in the form of a powder particleswherein the components of the composition are applied to a substrate toproduce a coated article.

Powder Coating Composition

In another related embodiment of the present invention, the instantinvention is an epoxy resin powder coating composition comprising (a)particles of a reaction product of (i) a compound having at least onevicinal epoxy group and (ii) an amino alcohol; and (b) particles of acompound having at least one vicinal epoxy group.

The epoxy resin hardener composition (curing agent) of the presentinvention may be utilized with an epoxy resin to form a curable powdercoating composition which may optionally include adjuncts known in theart such as pigments, fillers, dyes and flow control agents. In oneembodiment, the powder coating composition of the present inventioncomprises one or more of a pigment, a filler, a dye or a flow controlagent.

The powder coating composition of the present invention may be preparedby any process which blends the components of the compositionsubstantially uniformly. For example, dry blend, semi-dry blend or meltblend procedures may be used. The blend can then be pulverized to formthe powder coating composition. Particles of the powder coatingcomposition will preferably have a size of not more than about 300microns.

The epoxy resin powder coating composition, which includes the hardenercomposition of the present invention, may be applied to a substrate byany desired powder coatings process application method known in the art.Examples of application methods for applying the powder coatingcomposition of the present invention to a substrate include fluidizedbed sintering (FBS), electrostatic powder coating (EPC) andelectrostatic fluidized bed (EFB) applications.

In the fluidized bed sintering (FBS) process a preheated substrate, suchas for example a metal pipe, is immersed into the powder coatingcomposition, which is kept suspended by a flow of air. The substrate tobe coated is preheated to a temperature, for example in one embodimentof at least about 200° C., and in another embodiment of at least about240° C., but generally not higher than to about 350° C. in oneembodiment, and in another embodiment, not higher than about 300° C. Thepreheated substrate may then be contacted with the fluidized bed (forexample, immersed therein). The immersion time of the substrate depends,inter alia, on the desired coating thickness.

In the electrostatic powder coating (EPC) process, the powder coatingcomposition is blown by compressed air into an applicator where it isusually charged with a voltage of about 30 to 100 kV by a high-voltagedirect current, and sprayed onto the surface of the substrate to becoated. Then the coated substrate is baked in a suitable oven. Thepowder adheres to the cold substrate due to its charge. Alternatively,the electrostatically charged powder can be sprayed onto a heatedsubstrate such as a pipe and allowed to cure with the residual heat ofthe substrate or with the help of external heat.

In the electrostatic fluidized bed (EFB) process, the above proceduresare combined by mounting annular or partially annular electrodes over afluidized bed containing the powder so as to produce an electrostaticcharge of, for example, 50 to 100 kV. Substrates are heated attemperatures specific for the powder coating to fully cure.

The coating processes above are used to ensure that each powder particlecomprises all of the components that are necessary to obtain a completecure and attain the stated performance properties.

Numerous substrates can be coated with the powder coating composition ofthe present invention. The preferred substrates are metals (for example,iron, steel, copper), in particular metal pipes. Examples of othermaterials that may be coated with the powder coating composition of thepresent invention include ceramic and glass materials. The coating madefrom the powder coating composition of the present invention may finduse, for example, as coating material for pipelines operating at highservice temperatures (for example, about 110° C. and higher).

The sintered and non-sintered resins as well as the coating compositionof the present invention can be also used to electrically insulatecoils, transformers, and motors by coating the armatures and stators.The coating composition may also be used to coat magnet wire, bus bars,and torpid cores. Among other things, the above coating composition maybe used by manufacturers of appliance fractional horsepower motors andother applications requiring UL Electrical Insulation Systemsrecognition. In addition, properly formulated, the thermosettable epoxyresin compositions of the present invention can also be used inelectrical laminate applications.

In order to provide a better understanding of the present inventionincluding representative advantages thereof, the following examples areoffered. It should be understood that the following examples are forillustrative purposes and should not be regarded as limiting the scopeof the present invention to any specific materials or conditions.

Example 1

To 101.4 g of 2-amino-2-hydroxymethyl-1,3-propanediol (THMAM) in areactor is slowly added 40 g of commercially available diglycidyl etherof bisphenol A (DER 330 brand epoxy resin from The Dow Chemical Company)with a dropping funnel to obtain slurry that is brought to reaction byheating up to 168° C. To the resulting stirred homogeneous mixture isadded 60 g of DER 330 brand epoxy resin over a period of 30 minutesduring which time the reactor's temperature is maintained between 160°C. (set temperature) and 177° C. (by reaction exotherm) followed bystirring for an additional 30 minutes at a temperature of 160° C. toensure more complete reaction. The glass transition point for theresulting product is 37° C. The melt viscosity at 150° C. of the productis 2.1 Pa·s. The softening point of the product is 81° C.

Example 2

To 324.5 g of 2-amino-2-hydroxymethyl-1,3-propanediol (THMAM) in areactor at a temperature of 172° C. is slowly added 480 g of acommercially available diglycidyl ether of bisphenol A (DER 330 brandepoxy resin from The Dow Chemical Company) with a dropping funnel duringwhich time the reactor's temperature is maintained between 153° C. and172° C. followed by stirring for an additional 30 minutes at atemperature of 150° C. to ensure more complete reaction. The glasstransition point for the resulting product is 56° C. The melt viscosityat 150° C. of the product is 2.7 Pa·s. The softening point of theproduct is 96° C. No unreacted epoxy groups are observed by ¹³C NMR. Theapproximate mass distribution by ¹³C NMR is BAB 84 mole %; B 10 mole %;BABAB 6 mole %; wherein A is DER 330 and B is THMAM.

Example 3

To 167.3 g of 2-amino-2-hydroxymethyl-1,3-propanediol (THMAM) in areactor at a temperature of 175° C. is slowly added 333 g of acommercially available diglycidyl ether of bisphenol A (DER 330 brandepoxy resin from The Dow Chemical Company) with a dropping funnel duringwhich time the reactor's temperature is maintained between 156° C. and178° C. followed by stirring for an additional 60 minutes at atemperature of 175° C. to ensure more complete reaction. The glasstransition point for the resulting product is 78° C. The melt viscosityat 150° C. of the product is 131 Pa·s. The softening point of theproduct is 134° C.

Example 4

To 145 g of 2-amino-2-hydroxymethyl-1,3-propanediol (THMAM) in a reactorat a temperature of 172° C. is slowly added first 18.5 g of a liquidepoxy resin based on polyglycol diglycidyl ether and then 204.5 g of acommercially available diglycidyl ether of bisphenol A (DER 330 brandepoxy resin from The Dow Chemical Company) with a dropping funnel duringwhich time the reactor's temperature is maintained between 168° C. and182° C. followed by stirring for an additional 30 minutes at atemperature of 175° C. to ensure more complete reaction. The glasstransition point for the resulting product is 40° C. The melt viscosityat 150° C. of the product is 2.4 Pa·s. The softening point of theproduct is 91° C.

Example 5

To 142 g of 2-amino-2-hydroxymethyl-1,3-propanediol (THMAM) in a reactorat a temperature of 165° C. is slowly added first 23 g of a liquid epoxyresin based on polyglycol diglycidyl ether and then 200 g of acommercially available diglycidyl ether of bisphenol A (DER 330 brandepoxy resin from The Dow Chemical Company) with a dropping funnel duringwhich time the reactor's temperature is maintained between 160° C. and181° C. followed by stirring for an additional 30 minutes at atemperature of 170° C. to ensure more complete reaction. The glasstransition point for the resulting product is 49° C. The melt viscosityat 150° C. of the product is 4.0 Pa·s. The softening point of theproduct is 98° C.

Examples 6 and 7 and Comparative Example A

Three powder coating compositions are prepared by blending the componentpowders shown in Table I below.

TABLE I Comparative Component in Powder Example A Example 6 Example 7Coating Composition wt % wt % wt % Epoxy Resin A⁽¹⁾ 11.8 11.0 12.0 EpoxyResin B⁽²⁾ 17.7 16.4 18.0 Epoxy Resin C⁽³⁾ 29.5 27.4 30.1 Prior ArtEpoxy Resin 14.5 — — Hardener⁽⁴⁾ Product of Example 2 — 15.8 10.4Accelerator⁽⁵⁾ — 3.46 3.46 2-Methylimidazole 1.5 Flow Modifier⁽⁶⁾ — 1 1BaSO4 Powder 20 20 20 TiO2 Powder 5 5 5 Total Wt % Components 100.0100.0 100.0 E/XH Ratio⁽⁷⁾ 1.4 1.4 1.4 Notes for Table I: ⁽¹⁾Epoxy ResinA is a solid modified bisphenol A epoxy resin containing 10 wt % novolacmultifunctional epoxy resin commercially available from The Dow ChemicalCompany and sold under the trademark DER 6615. ⁽²⁾Epxoy Resin B is abisphenol A based solid epoxy resin commercially available from The DowChemical Company and sold under the trademark DER 664UE. ⁽³⁾Epoxy ResinC is a solid modified bisphenol A epoxy resin containing 18.7 wt %Novolac multifunctional epoxy resin commercially available from The DowChemical Company and sold under the trademark DER 642-U20. ⁽⁴⁾Prior ArtEpoxy Resin Hardener is a phenolic epoxy resin hardener commerciallyavailable from The Dow Chemical Company and sold under the trademark DEH85. ⁽⁵⁾Accelerator is a 2-methylimidazole based accelerator commerciallyavailable from Hexion Speciality Chemicals Company and sold under thetrademark Epon P101. ⁽⁶⁾Flow Modifier is a surface tension modifiercommercially available from Cytec and sold under the trademark MODAFLOW.⁽⁷⁾E/HX Ratio is the ratio of the equivalents of epoxy groups over thesum of equivalents of aminohydrogen groups and phenol groups in theuncured formulation.

The powder coating compositions described in Table I above are appliedto grit blasted steel panels and cured at 170° C. for 3 minutes. Theapplied coatings have a thickness of about 0.35 millimeters. Thecoatings are subjected to a hot water coating adhesion test and acathodic disbondment test (CAN/CAS-Z245.20-M92). The results of thetests are shown in Table II below.

TABLE II Test and Properties Hot Water Coating Adhesion Rating 5 1 1Test (at 75° C., for 48 hours) % removed 100% 5-10% 5-10% CathodicDisbondment Test mm removed 28 mm 5 mm 4-6 mm (28 days, 40 mm cell) (indiameter)

It should be readily apparent that although the present invention hasbeen described above in relation with its preferred embodiments, itshould be understood by those of ordinary skill in the art that thepresent invention is not limited thereby but is intended to cover allalternatives, modifications and equivalents that are included within thescope of the present invention as defined by the following claims.

What is claimed is:
 1. A solid amino functional hardener compositioncomprising a reaction product of: (i) a compound having at least onevicinal epoxy group; and (ii) an amino alcohol having at least one aminogroup and at least one alcohol group, where the at least one amino groupof the amino alcohol are primary amino groups and a mole ratio of aminegroups of the amino alcohol is in excess of the epoxy groups of thecompound having at least one vicinal epoxy group in the range of from25:1 to 3:1.
 2. The solid amino functional hardener composition of claim1, wherein the amino alcohol is an amino polyol.
 3. The solid aminofunctional hardener composition of claim 1, wherein the amino alcohol isselected from the group consisting of monoethanolamine,2-amino-2-hydroxymethyl-1,3-propanediol and2-amino-2-methyl-1,3-propanediol.
 4. The solid amino functional hardenercomposition of claim 1, wherein the compound having at least one vicinalepoxy group comprises a compound having two vicinal epoxy groups.
 5. Thesolid amino functional hardener composition of claim 1, wherein thecompound having at least one vicinal epoxy group comprises a compoundhaving the following formula:

wherein n is 0 or more.
 6. The solid amino functional hardenercomposition of claim 1 useful as a hardener for one or more of thecompounds selected from epoxy-, isocyanate-, carboxylic acid-, vinyl-and acrylic-functional resins.
 7. The solid amino functional hardenercomposition of claim 1, wherein the composition is dispersible in water.8. The solid amino functional hardener composition of claim 1, whereinthe composition has a softening point of from about 30° C. to about 150°C.